Thermofix process for the dyeing of polyester fibers

ABSTRACT

Polyester is dyed through thermofixation in fast shades with azo dyestuffs of the formula ##SPC1## 
     Wherein 
     R 1  is hydrogen, chlorine, bromine, lower alkyl, or lower alkoxy; 
     R 2  is hydrogen, chlorine, bromine, lower alkyl, lower alkoxy, R 7  CONH-- or R 7  SO 2  NH--; 
     R 3  is hydrogen, lower alkyl, hydroxy(lower alkyl), lower alkoxy(lower alkyl), cyano(lower alkyl), chloro(lower alkyl), bromo(lower alkyl) or ##EQU1## R 4  is hydrogen, lower alkyl, hydroxy(lower alkyl), lower alkoxy(lower alkyl), cyano(lower alkyl), chloro(lower alkyl), bromo(lower alkyl), benzyl, chlorobenzyl, bromobenzyl, nitrobenzyl or ##EQU2## one of R 5  and R 6  is hydrogen or methyl; AND THE OTHER R 5  and R 6  is hydrogen; 
     Each R 7  is independently lower alkyl, chloro(lower alkyl) bromo(lower alkyl), cyano(lower alkyl), phenyl, chlorophenyl, bromophenyl, lower alkylphenyl, lower alkoxyphenyl or cyanophenyl; 
     X is hydrogen, chlorine, bromine, lower alkyl, lower alkoxy, hydroxy(lower alkyl) or lower alkoxy(lower alkoxy); 
     Y is hydrogen, chlorine, or bromine; and 
     Z is methylene or carbonyl.

This is a division of application Ser. No. 241,810, filed Apr. 6, 1972,now U.S. Pat. No. 3,884,901.

BACKGROUND OF THE INVENTION

Azo dyes bearing water solubilizing groups have long been known asdyestuffs for natural polyamide fibers. Typically such azo dyes havecontained at least one sulfonic acid group, although a relatively minoramount of the research in azo dyes for natural polyamide fibers has beendevoted to sulfonic acid-free azo dyes which contain at least onecarboxylic acid group. It is generally recognized in the art that suchazo dyes are generally unsuited for the dyeing of synthetic fibers suchas polyethylene terephthalate.

We have now discovered a novel dyeing process which makes use of thethermofixation process and a specific class of azo dyes which yieldsexcellent dyeings on polyesters, particularly polyethyleneterephthalate, with azo dyes containing a free carboxylic acid group.

SUMMARY OF THE INVENTION

In accordance with the invention there are provided polyester dyeingswith compounds of the formula: ##SPC2##

Wherein

R₁ is hydrogen, chlorine, bromine, lower alkyl, or lower alkoxy;

R₂ is hydrogen, chlorine, bromine, lower alkyl, lower alkoxy, R₇ -CONH--or R₇ SO₂ NH--;

R₃ is hydrogen, lower alkyl, hydroxy(lower alkyl), lower alkoxy(loweralkyl), cyano(lower alkyl), chloro (lower alkyl), bromo(lower alkyl) or##STR1## R₄ is hydrogen, lower alkyl, hydroxy(lower alkyl), loweralkoxy(lower alkyl), cyano(lower alkyl), chloro(lower alkyl),bromo(lower alkyl), benzyl, chlorobenzyl, bromobenzyl, nitrobenzyl or##STR2## one of R₅ and R₆ is hydrogen or methyl; and the other R₅ and R₆is hydrogen;

each R₇ is independently lower alkyl, chloro(lower alkyl), bromo(loweralkyl), cyano(lower alkyl), phenyl, chlorophenyl, bromophenyl, loweralkylphenyl, lower alkoxyphenyl or cyanophenyl;

X is hydrogen, chlorine, bromine, lower alkyl, lower alkoxy,hydroxy(lower alkyl) or lower alkoxy(lower alkoxy);

Y is hydrogen, chlorine, or bromine; and

Z is methylene or carbonyl.

DETAILED DESCRIPTION

As the starting material for the preparation of the azo dyestuffs(I) maybe mentioned a base of the formula ##SPC3##

wherein X, Y and Z are as defined above. The base (II) is converted to adiazotized base of the formula ##SPC4##

wherein X, Y and Z are as defined above and An⁻ is anion. To produce theazo dyestuffs(I), the diazotized base (III) is treated with a coupler ofthe formula ##SPC5##

wherein R₁, R₂, R₃ and R₄ are as defined above.

A convenient diazotization method involves treating the base (II) incold water containing enough hydrochloric acid to make the mediumstrongly acidic and adding thereto an amount of sodium nitrite at leaststoichiometrically equivalent to the amount of base, the reaction massbeing maintained at or near the temperature of melting ice. A surfaceactive material with emulsifying properties may advantageously be used.The diazotized base is essentially soluble in the acid medium providedthe volume is adequate.

Another diazotization method involves dissolving sodium nitrite inconcentrated sulfuric acid, heating to a temperature of about 60°-70° C,cooling the resulting solution to 0°-10° C and adding thereto the base(II).

The azo dyestuffs (I) are made by the reaction of the diazotized base(III) with the coupler (IV) by adding the diazonium salt to a coldaqueous acidic solution of the coupler. A buffering agent, such assodium acetate may be added to reduce the acidity to a pH of 5 to 7 .The mixture is allowed to react for up to several hours at roomtemperature and is thereafter filtered and washed acid free. The desiredazo dyestuff (I) is thus obtained in the form of a wet cake.

It may be noted that in the particular cases where R₃ and R₄ aretogether desired to be hydrogen, it is often advantageous to convert thecoupler (IV) to the arylaminomethanesulfonic acid salt (V) through theuse of formaldehyde and sodium bisulfite in known manner. ##SPC6##

Coupling may then be carried out in the usual way. After formation ofthe monoazo body, hydrolysis of the alkylenesulfo moiety can be broughtabout by gentle heating in dilute aqueous alkali, forming the azodyestuff (I) in which R₃ = R₄ = H. (The dyestuff is somewhat soluble indilute aqueous alkali due to the carboxylic group. Neutralization of thehydrolysis medium facilitates isolation of the azo dyestuff (I) ). Themethod is especially useful in those cases in which R₁ is hydrogen,alkyl, chlorine or bromine, and often helpful in achieving better yieldswhen R₁ is alkoxyl.

The products produced from the coupling reaction, when suitablydispersed, are excellent dyes for polyester fabrics, and areparticularly suited for dyeing polyester by thermofixation methods.

To prepare the product for application to the polyester substrates theproduct must be suitably dispersed. This may be done in any of severalwell-known methods, milling as in a ball-mill with dispersing agentssuch as lignin sulfonic acid materials, for instance. The resultantaqueous dispersion can be dried, as in a spray-dryer, or preserved andused as a paste. Standardization to any desired lower strength can bedone with inert colorless diluents such as inorganic salts for powders,or water for pastes. Other materials such as preservatives, foam-controlagents, and wetting agents may be added as desired.

Dispersed pastes are made by wet milling the dye in conventionalequipment in the presence of a dispersing agent, preferably sodiumlignin sulfonate or sodium alkylnaphthalene sulfonate. Various othercommercially available dispersing agents, such as sodium salts ofcarboxylated polyelectrolytes and the naphthalene sulfonates; e.g., thecondensation products of sulfonated naphthalene and formaldehyde, suchas sodium dinaphthylmethane disulfonate, are conveniently used. The oildisperse paste may be cut or standardized to a standard strength withwater. The final color content of the finished paste averages from 10-40percent by weight (pure color) active dye base.

Disperse powders are prepared by wet milling color in the presence of adispersant, such as those mentioned hereabove, in equipment such as aball-mill, Werner-Pfleiderer mill or attritor. The dispersed material isoven or spray dried and micropulverized if necessary to provide thedispersed powder. The color is cut or standardized to a standardstrength in a blender with a diluent, such as sodium sulfate or dextrin.A wetting agent, such as sodium cetyl sulfate or an alkylphenoxypolyethanol may be added to aid in wetting out the product when it isplaced in the dye bath. Disperse powders are usually cut or standardizedto 25-60 percent by weight color content (pure color).

The dye is preferably applied to the aromatic polyester fiber bythermofixation methods, such as the "Thermosol" process. This processinvolves padding the cloth with a dilute dye dispersion, followed bydrying to remove water (e.g., by preheating with infrared heat) andcuring by dry heat fixation using dried hot air or heated contact rolls.Curing or fixation temperatures of 350°-430° F are used for less than 2minutes, usually for 30 to 90 seconds. Ordinarily, if the padded fabricis entirely polyester, curing is done at 400°-430° F. If the fabriccontains cotton or viscose rayon, apart from synthetic fibers, there islittle danger of damaging cellulosic portions, but if wool is present,the curing temperature must be kept below 357° F and the time must bereduced to about 30 seconds.

For durable press finishing of mixed polyester-cotton blends, afterthermofixation the residual unfixed dye is removed from the fabric byscouring and the cleaned fabric is given a durable press cure at300°-350° F. The new dyes of the invention show an excellent diffusionrate in the polyester fibers at the dyeing temperature and a lowdiffusion rate at the preferred press curing temperature of 300°-350° F.

In order to evaluate the effectiveness of a particular dye for a giventype of fiber, the dyed fiber is examined for substantivity of thecolor, light fastness of the color, and resistance of the color tosublimation. Specific tests for the evaluation of these importantproperties are described in the examples that follow.

The invention is further illustrated by the following examples:

EXAMPLE I ##SPC7##

    __________________________________________________________________________    A. Diazo                                                                               There is charged to a 3000 ml. beaker                                300.0 ml.                                                                              water                                                                60.0 g.  hydrochloric acid (32%)                                              55.1 g.  4'-chloro-3'-amino-o-benzoylbenzoic acid (0.2 mole) and               5.0 g.  "Tween 20" (a commercially available surface active material).                The mixture is heated to 80° C, allowed to stir and cool               to                                                                            30° C and iced to 0° C. At 0-5° C there is               added to the mixture,                                                         during a period of 15 minutes, a solution of                         15.0 g.  sodium nitrite dissolved in                                           50.0 ml.                                                                              cold water.                                                                   The diazotization mixture is stirred 2 hours at 0-5° C,                then the                                                                      excess nitrous acid is destroyed with sulfamic acid and the                   diazo clarified and kept at 0-5° C.                           B. Coupler                                                                             A 4000 ml. beaker is charged with                                    400.0 ml.                                                                              water at 60° C                                                25.0 g.  N,N-dimethylaniline (0.206 mole) and                                 30.0 g.  hydrochloric acid (32%).                                                      The mixture is stirred to complete solution and iced to                       0° C.                                                         C. Coupling                                                                            The diazo solution is added to the coupler solution at                        0≅5° C.                                                      The mixture is stirred sixteen hours, during which time the                   temperature is allowed to rise to that of the room. The solids                are then isolated by filtration and the filter cake is washed                 acid free and dried.                                                          Yield: 77.0 g.; 95.5% (0.2 mole = 81.5 g.)                           D. Dispersion                                                                          A laboratory ball-mill is charged with                               60.0 g.  dry color (A, above)                                                 58.0 g.  "Lignosol FTA" (a commercially available ligninsulfonic acid                  dispersing agent) and                                                282.0 ml.                                                                              cold water.                                                                   The mixture is ball-milled for 12 hours. A paste of 15% color                 content was obtained.                                                         Dispersion: adequate, as shown by filter tests.                      E. Evaluation:                                                                         When applied to polyethylene terephthalate by the recognized                  method (carrier, pressure, thermofixation) golden yellow hues                 of excellent light fastness and sublimation fastness are                      obtained.                                                                     The dye is especially suitable for thermofixation                    __________________________________________________________________________             dyeing.                                                          

EXAMPLE II ##SPC8##

    __________________________________________________________________________    A. Diazo                                                                               There is charged to a 3000 ml. beaker                                300.0 ml.                                                                              water                                                                60.0 g.  hydrochloric acid (32%)                                              55.1 g.  4'-chloro-3'-amino-o-benzoic acid (0.2 mole) and                      5.0 g.  "Tween 20".                                                                   The mixture is heated to 80° C, allowed to stir and cool               to                                                                            30° C and iced to 0° C. At 0-5° C there is               added to the mixture,                                                         during a period of 15 minutes, a solution of                         15.0 g.  sodium nitrite dissolved in                                          50.0 ml. cold water.                                                                   The diazotization mixture is stirred 2 hours at 0-5° C,                then                                                                          the excess nitrous acid is destroyed with sulfamic acid and the               diazo clarified and kept at 0°5° C.                    B. Coupler                                                                             A 4000 ml. beaker is charged with                                    200.0 g. ice,                                                                 200.0 ml.                                                                              water,                                                               67.6 g.  2,2'(3-acetamidophenylimino)diethanol diacetate (0.21 mole),         40.0 g.  hydrochloric acid (32%) and                                          50.0 g.  acetic acid.                                                                  The mixture is stirred to solution and iced to 0° C.          C. Coupling                                                                            Coupling is carried out in the way described in Example I,                    Part C.                                                                       Yield: 111.0 g. 91% (0.2 mole = 121.6 g.)                            D. Dispersion                                                                          A laboratory ball-mill is charged with                               60.0 g.  monoazo material, (part C, above)                                    58.0 g.  "Lignosol FTA" and                                                   282.0 ml.                                                                              cold water.                                                                   The mixture is milled for 12 hours. A disperse paste containing               15% of dye base is obtained. The dispersion is satisfactory                   as shown by filter tests.                                            E. Evaluation:                                                                         Dyeings of clear red hues are obtained by treating polyethylene               terephthalate fabric in known manners with the dispersion from                D above. The dye dispersion is especially well suited for                     thermofix dyeing. Resistance to sublimation is outstandingly                  good.                                                                __________________________________________________________________________

EXAMPLE III ##SPC9##

    __________________________________________________________________________    A. Diazo                                                                               There is charged to a 3000 ml. beaker                                350.0 ml.                                                                              water                                                                60.0 g.  hydrochloric acid (32%)                                              54.2 g.  4'-methoxy-3'-amino-o-benzoylbenzoic acid (0.2 mole) and             4.0 g.   "Tween 20".                                                                   The mixture is heated to 70° C, allowed to stir and cool               to                                                                            30° C and iced to 0° C. At 0-5° C there is               added to the mixture,                                                         during a period of 15 minutes, a solution of                         15.0 g.  sodium nitrite dissolved in                                          50.0 ml. cold water.                                                                   The diazotization mixture is stirred 3 hours at 0- 5° C.               Then                                                                          the excess nitrous acid is destroyed with sulfamic acid and the               diazo clarified and kept at 0-5° C.                           B. Coupler                                                                             A 4000 ml. beaker is charged with                                    400.0 ml.                                                                              water at 60° C                                                25.0 g.  N,N-dimethylaniline (0.206 mole) and                                 30.0 g.  32% hydrochloric acid.                                                        The mixture is stirred to complete solution and iced to                       0° C.                                                         __________________________________________________________________________

C. Coupling

The coupling of the materials from Part A and Part B is carried out inthe manner described in Example I, Part C. Yield: 71.-g. 88% (0.2 mole =80.6 g.)

D. Dispersion

A 15% color content disperse paste is made in the manner described inExample I, Part D.

E. Evaluation

Dyeings on polyethylene terephthalate fabric produced by the dispersepaste, Part D above, in established ways show clear scarlet dyeings ofgood properties, especially in resistance to sublimation.

EXAMPLE IV ##SPC10##

A. Diazc

A diazonium solution is prepared exactly in the manner of Example I,Part A.

B. Coupler

A coupler solution is prepared exactly in the way described in ExampleI, Part B, except that 30.6 g. N,N-diethylaniline (M.W. 149; 0.205 mole)is used instead of N,N-dimethylaniline.

C. Coupling

The diazonium salt and the coupler are combined exactly in the waydescribed in Example I, Part C, and the product isolated and treatedsimilarly. The dry weight of the monoazo body produced is 84.5 g, or 97%of the theoretical yield of 87.0 g.

D. Dispersion

A 15% disperse paste is prepared in the way described in Example I, PartD.

E. Evaluation

Dyeings of the disperse paste (Part D, above) on polyethyleneterephthalate fabric show a clear yellowish orange hue. Properties arevery like those of the product of Example I, being excellent in fastnessto light and to sublimation. The dye gives excellent color yield whendyed by the thermofixation method.

EXAMPLES V-LVII

By substituting an equimolar amount of the base (II) for the3'-amino-4'-chloro-o-benzoylbenzoic acid and an equimolar amount ofcoupler (IV) for the N,N-dimethylaniline of Example I, otherwisefollowing the procedure of Example I, azo dyestuffs (I) which dyepolyethylene terephthalate via thermofixation in the shade indicated areobtained.

    __________________________________________________________________________                                                             Hue on                                                                        Polyethy-                                                                     lene Tere            EX.  X     Y  Z   R.sub.1                                                                           R.sub.2    R.sub.3       R.sub.4   phthalate            __________________________________________________________________________    V    Cl    H  CO  H   H          CH.sub.2 CH.sub.2 OH                                                                        CH.sub.2 CH.sub.2 OH                                                                    Orange               VI   Cl    H  CO  H   H          C.sub.2 H.sub.5                                                                             CH.sub.2 CH.sub.2 CN                                                                    Orange               VII  Cl    H  CH.sub.2                                                                          H   H          CH.sub.3      CH.sub.3  Reddish                                                                       yellow               VIII OCH.sub.3                                                                           H  CH.sub.2                                                                          H   H          CH.sub.2 CH.sub.2 CN                                                                        CH.sub.2 CH.sub.2 CN                                                                    scarlet              IX   Br    H  CO  H   H          CH.sub.2 CH.sub.2 CN                                                                        H         orange               X    Cl    H  CO  H   NHCOCH.sub.3                                                                             C.sub.2 H.sub.5                                                                             C.sub.2 H.sub.5                                                                         scarlet              XI   Cl    H  CO  CH.sub.3                                                                          H          CH.sub.2 CH.sub.2 OH                                                                        CH.sub.2 CH.sub.2 OH                                                                    orange               XII  H     H  CO  OCH.sub.3                                                                         CH.sub.3   CH.sub.2 CH.sub. 2 OH                                                                       CH.sub.2 CH.sub.2 OH                                                                    reddish                                                                       orange               XIII H     H  CO  OCH.sub.3                                                                         OCH.sub.3  CH.sub.2 CH.sub.2 OH                                                                        CH.sub.2 CH.sub.2 OH                                                                    dull                                                                          red                  XIV  Cl    H  CO  OC.sub.2 H.sub.5                                                                  NHCOCH.sub.3                                                                             CH.sub.2 CH.sub.2 OCOCH.sub.3                                                               CH.sub.2 CH.sub.2 OCOCH.sub                                                   .3        bordeaux             XV   Cl    H  CO  OCH.sub.3                                                                         NHCOCH.sub.3                                                                             CH.sub.2 CH.sub.2 OCOC.sub.2 H.sub.                                                         CH.sub.2 CH.sub.2 OCOC.sub.                                                   2 H.sub.5 bordeaux             XVI  Cl    H  CH.sub.2                                                                          OC.sub.2 H.sub.5                                                                  NHCOCH.sub.3                                                                             CH.sub.2 CH.sub.2 CN                                                                        C.sub.2 H.sub.5                                                                         rubine               XVII Cl    H  CO  OC.sub.2 H.sub.5                                                                  NHCOCH.sub.3                                                                             CH.sub.2 CH.sub.2 OCOCH.sub.2 Cl                                                            CH.sub.2 CH.sub.2 OCOCH.sub                                                   .2 Cl     bordeaux             XVIII                                                                              CH.sub.3                                                                            H  CO  H   H          CH.sub.3      CH.sub.3  orange               XIX  C.sub.2 H.sub.5                                                                     H  CO  H                                                                                  ##STR3##  CH.sub.2 CH.sub.2 OCOCH.sub.3                                                               CH.sub.2 CH.sub.2 OCOCH.sub                                                   .3        dull red             XX   Cl    H  CO  OCH.sub. 3                                                                        CH.sub.3   CH.sub.2 CH.sub.2 Br                                                                        CH.sub.2 CH.sub.2 CN                                                                    red                  XXI  H     H  CO  OCH.sub.3                                                                         OCH.sub.3  H             H         yellowish                                                                     red                  XXII Cl    H  CO  H                                                                                  ##STR4##  CH.sub.2 CH.sub.2 OH                                                                        CH.sub.2 CH.sub.2 OH                                                                    red                  XXIII                                                                              Cl    H  CO  OCH.sub.3                                                                         H          H             H         yellowish                                                                     orange               XXIV Cl    H  CO  H   Cl         C.sub.2 H.sub.5                                                                             C.sub.2 H.sub.5                                                                         orange               XXV  Cl    H  CO  OCH.sub.3                                                                         NHSO.sub.2 CH.sub.3                                                                       ##STR5##     CH.sub.2 CH.sub.2 OCOC.sub.                                                   2 H.sub.5 plum                 XXVI Cl    H  CO  H   Br         CH.sub.3      CH.sub.3  reddish                                                                       orange               XXVII                                                                              Br    H  CO  OC.sub.2 H.sub.5                                                                  OC.sub.2 H.sub.5                                                                         CH.sub.2 CH.sub.2 OH                                                                        CH.sub.2 CH.sub.2 OH                                                                    bluish                                                                        red                  XXVIII                                                                             Cl    H  CO  H                                                                                  ##STR6##                                                                                 ##STR7##     CH.sub.2 CH.sub.2 OCOCH.sub                                                   .3        red                  XXIX H     H  CO  H   H          CH.sub.2 CH.sub.2 CN.sub.2 CH.sub.3                                                         CH.sub.2 CH.sub.2 CN                                                                    reddish                                                                       yellow               XXX  Cl    H  CO  H   H          CH.sub.2 CH.sub.2 OCH.sub.3                                                                 CH.sub.2 CH.sub.2 OCH.sub.3                                                   .         orange               XXXI Cl    H  CO  H   H          CH.sub.2 CH.sub.2 Cl                                                                        CH.sub.2 CH.sub.2 CN                                                                    orange               XXXII                                                                              Cl    H  CO  H                                                                                  ##STR8##  CH.sub.2 CH.sub.2 OCOCH.sub.3                                                               CH.sub.2 CH.sub.2 COCH.sub.                                                   3         red                  XXXIII                                                                             Cl    H  CO  H   H          CH.sub.3 CH.sub.2 OCOC.sub.3 H.sub.7                                                        CH.sub.3  orange               XXXIV                                                                              Cl    H  CO  H   H          CH.sub.2 CH.sub.2 OCOCH.sub.2 CN                                                            C.sub.2 H.sub.5                                                                         orange               XXXV Cl    H  CO  H   H          CH.sub.2 CH.sub.2 OCOCH.sub.2 Br                                                            CH.sub.2 CH.sub.3                                                                       orange               XXXVI                                                                              H     Cl CO  H   CH.sub.3   CH.sub.2 CH.sub.2 OH                                                                        CH.sub.2 CH.sub.2 CN                                                                    yellowish                                                                     scarlet              XXXVII                                                                             Cl    Cl CO  H   H          CH.sub.3      CH.sub.3  orange               XXXVIII                                                                            OCH.sub.3                                                                           H  CO  Br  H          CH.sub.2 CH.sub.2 CN                                                                        H         reddish                                                                       scarlet              XXXIX                                                                              H     Br CH.sub.2                                                                          OCH.sub.3                                                                          ##STR9##  CH.sub.2 CH.sub.2 OCOCH.sub.3                                                               CH.sub.2 CH.sub.2 OCOCH.sub                                                   .3        dull violet          XL   CH.sub.3                                                                            H  CO  OCH.sub.3                                                                          ##STR10## CH.sub.2 CH.sub.2 OCOCH.sub.3                                                               CH.sub.2 CH.sub.2 OCOCH.sub                                                   .3        dull violet          XLI  H     Br CO  H   H          C.sub.2 H.sub.5                                                                             C.sub.2 H.sub.5                                                                         orange               XLII OCH.sub.2--                                                                         H  CO  Cl  H          CH.sub.2 CH.sub.2 CN                                                                        CH.sub.3  scarlet                   CH.sub.2 OH                                                              XLIII                                                                              CH.sub.3                                                                            H  CO  OC.sub.2 H.sub.5                                                                   ##STR11## CH.sub.2 CH.sub.2 OCOC.sub.3 H.sub.7                                                        CH.sub.2 CH.sub.2 OCOC.sub.                                                   3 H.sub.7 bordeaux             XLIV H     H  CH.sub.2                                                                          OC.sub.2 H.sub.5                                                                  NHCOCH.sub.2 CN                                                                           ##STR12##    CH.sub.2 CH.sub.2 OCOCH.sub                                                   .3        bordeaux             XLV  OCH.sub.2 CH.sub.2--                                                                H  CH.sub.2                                                                          OCH.sub.3                                                                         OCH.sub.3  CH.sub.2 CH.sub.2 OH                                                                        CH.sub.2 CH.sub.2 OH                                                                    plum                      OCH.sub.3                                                                XLVI H     H  CO  H   NHCOCH.sub.2 Cl                                                                          CH.sub.2 CH.sub.2 OH                                                                        CH.sub.2 CH.sub.2 OH                                                                    red                  XLVII                                                                              (CH.sub.3).sub.2 CH                                                                 H  CO  H   H                                                                                         ##STR13##    CH.sub.3  orange               XLVIII                                                                             OCH.sub.3                                                                           Br CH.sub.2                                                                          H   NHCOCH.sub.2 Br                                                                          CH.sub.2 CH.sub.2 OCOCH.sub.3                                                               CH.sub.2 CH.sub.2 OCOCH.sub                                                   .3        bluish                                                                        red                  XLIX OCH.sub.3                                                                           H  CO  CH.sub.3                                                                          H          CH.sub.2 CH.sub.2 OCOCH.sub.3                                                               CH.sub.2 CH.sub.2 OCOCH.sub                                                   .3        red                  L    OCH.sub.3                                                                           H  CO  H                                                                                  ##STR14## CH.sub.2 CH.sub.2 OCOCH.sub.3                                                               CH.sub.2 CH.sub.2 OCOCH.sub                                                   .3        bluish red           LI   Cl    H  CO  OCH.sub.3                                                                          ##STR15##                                                                                ##STR16##    CH.sub.2 CH.sub.2 OCOCH.sub                                                   .3        bordeaux             LII  Cl    H  CO  OCH.sub.3                                                                         CH.sub.3                                                                                  ##STR17##    C.sub.2 H.sub.5                                                                         red                  LIII Cl    H  CO  H   H          C.sub.2 H.sub.5                                                                              ##STR18##                                                                              orange               LIV  Cl    H  CO  H   H          CH.sub.3                                                                                     ##STR19##                                                                              orange               LV   Cl    H  CO  H   H          C.sub.2 H.sub.5                                                                              ##STR20##                                                                              orange               LVI  H     H  CO  H   CH.sub.3   C.sub.4 H.sub.9                                                                              ##STR21##                                                                              scarlet              LVII Cl    H  CO  H   H          CH.sub.2 CH.sub.2 CN                                                                         ##STR22##                                                                              orange               __________________________________________________________________________

What is claimed is:
 1. Polyester dyed with a compound of the formula##SPC11##wherein R₁ is hydrogen or lower alkoxy; R₂ is hydrogen, loweralkoxy or R₇ CONH--; R₃ is lower alkyl, hydroxy(lower alkyl),cyano(lower alkyl) or --CH₂ CH₂ OCOR₇ ; R₄ is lower alkyl, hydroxy(loweralkyl), cyano(lower alkyl), or CH₂ CH₂ OCOR₇ ; R₇ is independently loweralkyl, bromo(lower alkyl), cyano(lower alkyl), phenyl, or chlorophenyl;X is hydrogen, chlorine, lower alkoxy, or lower alkoxy (lower alkoxy);and Y is hydrogen or bromine.
 2. Polyester dyed with a compound of theformula ##SPC12##wherein R₁ is hydrogen, chlorine, bromine, lower alkyl,or lower alkoxy; R₂ is hydrogen, chlorine, bromine, lower alkyl, loweralkoxy, R₇ CONH- or R₇ SO₂ NH-; R₃ is hydrogen, lower alkyl,hydroxy(lower alkyl), lower alkoxy(lower alkyl), cyano(lower alkyl),chloro(lower alkyl), bromo(lower alkyl), or ##STR23## R₄ is hydrogen,lower alkyl, hydroxy(lower alkyl), lower alkoxy(lower alkyl),cyano(lower alkyl), chloro(lower alkyl) bromo(lower alkyl), benzyl,chlorobenzyl, bromobenzyl, nitrobenzyl or ##STR24## one of R₅ and R₆ ishydrogen or methyl; and the other of R₅ and R₆ is hydrogen; each R₇ isindenpendently lower alkyl, chloro(lower alkyl), bromo (lower alkyl),cyano(lower alkyl), phenyl, chlorophenyl, bromophenyl, loweralkylphenyl, lower alkoxyphenyl or cyanophenyl; X is hydrogen, chlorine,bromine, lower alkyl, lower alkoxy, hydroxy(lower alkyl) or loweralkoxy(lower alkoxy); and Y is hydrogen, chlorine, or bormine. 3.Polyester dyed with a compound of claim 2 of the formula ##SPC13## 4.Polyester dyed with a compound of claim 2 of the formula ##SPC14## 5.Polyester dyed with a compound of claim 2 of the formula ##SPC15##